CN1984948A - Synergistic flame-proof mixtures for polystyrene foams - Google Patents

Synergistic flame-proof mixtures for polystyrene foams Download PDF

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Publication number
CN1984948A
CN1984948A CNA2005800237726A CN200580023772A CN1984948A CN 1984948 A CN1984948 A CN 1984948A CN A2005800237726 A CNA2005800237726 A CN A2005800237726A CN 200580023772 A CN200580023772 A CN 200580023772A CN 1984948 A CN1984948 A CN 1984948A
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styrene polymer
fire retardant
retardant
melt
peroxide
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CN1984948B (en
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K·哈恩
G·埃尔曼
J·鲁赫
M·阿尔门德英格
B·施密德
J·霍洛赫
P·施莫斯
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BASF SE
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/04—Oxygen-containing compounds
    • C08K5/14—Peroxides
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29B—PREPARATION OR PRETREATMENT OF THE MATERIAL TO BE SHAPED; MAKING GRANULES OR PREFORMS; RECOVERY OF PLASTICS OR OTHER CONSTITUENTS OF WASTE MATERIAL CONTAINING PLASTICS
    • B29B9/00—Making granules
    • B29B9/12—Making granules characterised by structure or composition
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C44/00—Shaping by internal pressure generated in the material, e.g. swelling or foaming ; Producing porous or cellular expanded plastics articles
    • B29C44/34—Auxiliary operations
    • B29C44/3461—Making or treating expandable particles
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
    • B29C48/25—Component parts, details or accessories; Auxiliary operations
    • B29C48/285—Feeding the extrusion material to the extruder
    • B29C48/29—Feeding the extrusion material to the extruder in liquid form
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
    • C08J9/0014—Use of organic additives
    • C08J9/0019—Use of organic additives halogenated
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
    • C08J9/04—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
    • C08J9/16—Making expandable particles
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/02—Halogenated hydrocarbons
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L25/00—Compositions of, homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring; Compositions of derivatives of such polymers
    • C08L25/02—Homopolymers or copolymers of hydrocarbons
    • C08L25/04—Homopolymers or copolymers of styrene
    • C08L25/06—Polystyrene
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29B—PREPARATION OR PRETREATMENT OF THE MATERIAL TO BE SHAPED; MAKING GRANULES OR PREFORMS; RECOVERY OF PLASTICS OR OTHER CONSTITUENTS OF WASTE MATERIAL CONTAINING PLASTICS
    • B29B9/00—Making granules
    • B29B9/02—Making granules by dividing preformed material
    • B29B9/06—Making granules by dividing preformed material in the form of filamentary material, e.g. combined with extrusion
    • B29B9/065—Making granules by dividing preformed material in the form of filamentary material, e.g. combined with extrusion under-water, e.g. underwater pelletizers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
    • B29C48/022—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor characterised by the choice of material
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
    • B29C48/03—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor characterised by the shape of the extruded material at extrusion
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
    • B29K2025/00—Use of polymers of vinyl-aromatic compounds or derivatives thereof as moulding material
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
    • B29K2105/00—Condition, form or state of moulded material or of the material to be shaped
    • B29K2105/0005—Condition, form or state of moulded material or of the material to be shaped containing compounding ingredients
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2203/00—Foams characterized by the expanding agent
    • C08J2203/12—Organic compounds only containing carbon, hydrogen and oxygen atoms, e.g. ketone or alcohol
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2203/00—Foams characterized by the expanding agent
    • C08J2203/14—Saturated hydrocarbons, e.g. butane; Unspecified hydrocarbons
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2325/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring; Derivatives of such polymers
    • C08J2325/02—Homopolymers or copolymers of hydrocarbons
    • C08J2325/04—Homopolymers or copolymers of styrene

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Manufacture Of Porous Articles, And Recovery And Treatment Of Waste Products (AREA)
  • Compositions Of Macromolecular Compounds (AREA)

Abstract

The invention relates to a method for the production of flame-proof, expandable styrene polymers (EPS) or flameproof styrene polymer extrusion foams (XPS). According to the invention, an organic bromine compound having a bromine content of at least 70 wt. % and a liquid peroxide, hydroperoxide or a peroxide solution as a flameproof agent is used as a flame-proof synergist.

Description

The Synergistic flame-proof mixtures that is used for polystyrene foam
The present invention relates to the method for a kind of production fp expandable styrene polymer (EPS) or fp styrene polymer exruded foams (XPS), the organbromine compound that wherein will have at least 70 weight % bromine contents is as fire retardant, and with superoxide or hydroperoxide liquid or peroxide solutions as retardant synergist.
For example, known by EP-A 0 981 574, WO 97/45477 or WO 03/46016 by extruding the method for the styrene polymer melt production fp expandable styrene polymer that contains whipping agent.Here, fire retardant (if suitable, together with other additive) and polystyrene fusion add whipping agent subsequently.
Here the used retardant synergist of halogenated fire-retardants such as hexabromocyclododecane (HBCD) is generally hot radical and forms thing, for example dicumyl peroxide or dicumyl.In extrusion, dicumyl peroxide and dicumyl can only add in the polystyrene substrate with pulverulent solids in the pressurized compartment.
In extrusion, because the result of the temperature peaks of the residence time and partial, shear-induced, the thermal stress on the thermo-responsive superoxide increases.Therefore, it is not fit closely having the superoxide of low transformation period 150 to 250 ℃ temperature.Therefore, although the dicumyl price is higher and efficient is lower, because it has the significantly higher transformation period, it is better than dicumyl peroxide as retardant synergist in the production of polystyrene exruded foams (XPS).
Expanded polystyrene foams with low especially residual benzene ethene and ethyl-benzene level is useful in many application.This comprises product and the foam molded articles in automobile is used with Food Contact.Low residue vinylbenzene and ethyl-benzene level reduce disadvantageous atomizing, and this is even more important for using in automotive field.
Be used for the suspension polymerization that EPS produces up to now, the low residue styrene content can only be realized by the long polymerization time under the high-temperature level.This has extremely adverse influence cycling time to polymerization.
Therefore, the method that the objective of the invention is to remedy above-mentioned deficiency and a kind of production fp expandable styrene polymer (EPS) and fp styrene polymer exruded foams (XPS) are provided wherein can be introduced retardant synergist simply and under the condition of gentleness.
Therefore, we have found that this paper starts the method for description.
Found molecular weight M wBe lower than 170000 styrene polymer and in granulation process, cause the polymkeric substance consume.The molecular weight that expandable styrene polymer preferably has is 190000 to 400000g/mol, especially is preferably 220000 to 300000g/mol.Owing to reduced by the molecular weight of shearing and/or heat causes, the molecular weight of expandable polystyrene is usually than the low approximately 10000g/mol of used polystyrene molecular weight.
In order to obtain very little pill, swelling at the die orifice of mould outlet should be very little.Having found that die orifice swells may especially be subjected to the influence of styrene polymer molecular weight distribution.Therefore, expandable styrene polymer should preferably have such molecular weight distribution, its polymolecularity M w/ M nBe not more than 3.5, especially preferred in 1.5 to 3 scope, very particularly preferably in 1.8 to 2.6 scope.
Used styrene polymer is the polystyrene (GPPS) of preferably transparent, impact resistant polystyrene (HIPS), anionoid polymerization polystyrene or impact resistant polystyrene (A-IPS), the styrene-multipolymer, acrylonitrile-butadiene-styrene (ABS) polymkeric substance (ABS), styrene-acrylonitrile (SAN), acrylonitrile-styrene-acrylic ester (ASA), methacrylic ester-butadiene-styrene (MBS), methyl methacrylate-acrylonitrile-butadiene-styrene (ABS) (MABS) polymkeric substance or its mixture or together with polyphenylene oxide (PPE).
In order to improve mechanical property or thermotolerance, mentioned styrene polymer can with the thermoplastic polymer blend, if the suitable expanding material that uses, described this thermoplastic polymer for example is a polyamide (PA), polyolefine such as polypropylene (PP) or polyethylene (PE), polyacrylic ester such as polymethylmethacrylate (PMMA), polycarbonate (PC), polyester such as polyethylene terephthalate (PET) or polybutylene terephthalate (PBT), polyethersulfone (PES), polyetherketone or polyether sulfides (PES) or its mixture, the ratio of this thermoplastic polymer is based on polymer melt, usually altogether up to 30 weight %, preferably in 1 to 10 weight % scope.In addition, for example also being fine in described weight range: hydrophobically modified or functionalized polymkeric substance or oligopolymer with the mixture of following material, rubber such as polyacrylic ester or polydiene, styrene-butadiene block copolymer for example, or biodegradable aliphatic series or aliphatic series/aromatic copolyesters.
The expanding material that is fit to for example for maleic anhydride modified styrol copolymer, contain the polymkeric substance of epoxide group or organosilane.
By mentioned thermoplastic polymer, especially the recycled materials formed of styrene polymer and expandable styrene polymer (EPS), can not add in the styrene polymer melt performance is not produced obvious dysgenic amount yet, described amount is not more than 50 weight % usually, especially 1 to 20 weight %.
The styrene polymer melt that contains whipping agent comprises equally distributed one or more whipping agents usually, and based on the styrene polymer melt that contains whipping agent, whipping agent is with 2 to 10 weight %, and the total amount of preferred 3 to 7 weight % exists.The whipping agent that is fit to is the conventional pneumatogen that is used for EPS, for example has the aliphatic hydrocrbon of 2 to 7 carbon atoms, alcohol, ketone, ether or halohydrocarbon.Preferred Trimethylmethane, normal butane, iso-pentane, the Skellysolve A of using.
In order to improve foaminess, inner water droplets in small, broken bits can be introduced in the styrene polymer matrix.This for example can realize by water being added in the fused styrene polymer matrix.The interpolation of water can be before whipping agent adds, simultaneously or afterwards, carry out in the part.The uniform distribution of water can be realized by dynamic or static mixer.
The styrene-based polymkeric substance, 0 to 2 weight %, the water yield of preferred 0.05 to 1.5 weight % is just enough usually.
Wherein at least 90% internal water be the expandable styrene polymer (EPS) of inner water droplets form of diameter 0.5 to 15 μ m in when foaming, form the hole with sufficient amount and the even foam of foamy structure.
The add-on of selecting whipping agent and water is so that the swelling capacity α of expandable styrene polymer (EPS) is not more than 125, and is preferred 25 to 100, and this swelling capacity α is defined as the tap density/foaming tap density afterwards before the foaming.
Expandable styrene polymer pill (EPS) produced according to the invention has the 700g/L of being not more than usually, preferably the tap density in 590 to 660g/L scopes.When using filler, depend on that the type of filler and amount tap density can appear in 590 to the 1200g/L scopes.
As fire retardant, use organbromine compound with at least 70 weight % bromine contents.Especially advantageously aliphatic series, cyclic aliphatic and aromatic bromine compound, for example hexabromocyclododecane, pentabromo-one chlorine hexanaphthene, penta-bromophenyl allyl ether.Styrene-based polymkeric substance, fire retardant consumption are generally 0.2 to 5 weight %, preferred 0.5 to 2.5 weight %.
The retardant synergist that is fit to is 6 minutes for the transformation period in 110 to 300 ℃ of temperature ranges, and preferably the transformation period is 6 minutes and is the formation of the hot radical in liquid or water soluble, hydrocarbon or white oil thing in 140 to 230 ℃ of temperature ranges.The pentane solution of preferred use ditertiary butyl peroxide (Trigonox  B), t-butyl hydroperoxide (Trigonox  A80), dicumyl peroxide or the aqueous solution of superoxide or hydroperoxide are as retardant synergist.Retardant synergist preferably uses with pure form, or under the solid situation, uses with (1 crust, 23 ℃) saturated in fact solution form under standard state, so that it can directly be metered in the chamber of heating and pressurization by typical pumping system.Retardant synergist is present in makes in the liquid phase that metering becomes possibility, to such an extent as to even under the situation of low decomposability superoxide, still have enough amounts and still can realize uniform mixing through processing or extrusion condition.Usually, the amount ranges of retardant synergist is 0.05 to 1 weight %, preferred 0.1 to 0.5 weight %.
Except water-soluble hydroperoxidation beyond the region of objective existence, method of the present invention also can be used for producing the fp expandable styrene polymer by suspension process.In suspension, but because pumping and be easy to homogenizing in organic phase, the use of liquid peroxide makes safety operation become possibility.
The inventive method is preferred for producing fp expandable styrene polymer (EPS), it is metered in the styrene polymer melt major ingredient stream that contains whipping agent by fire retardant and a certain proportion of styrene polymer melt premix in the side forcing machine is merged, and machine head plate is passed in the materials flow extruding that merges, and granulation is carried out under water subsequently.This retardant synergist preferably directly is metered in the major ingredient stream through the metering spray gun of pump and equal height.
Here, fire retardant and retardant synergist are at 140 to 220 ℃, and the residence time in preferred 170 to the 200 ℃ melt temperature scope can keep below 15 minutes.
In addition, the amount of superoxide/hydroperoxide that the molecular weight of polymer materials and VN can be by introducing forcing machine/static mixer is set.This can improve swellability and the special energy of material of EPS again.
And, for example can be with additive, nucleator, filler, softening agent, solubility and insoluble inorganic and/or organic dye and pigment by mixing machine or side forcing machine, for example, IR absorption agent such as carbon black, graphite or aluminium powder form join in the styrene polymer melt together or at different positions.Usually, the add-on of dyestuff and pigment is in 0.01 to 30 weight % scope, preferably in 1 to 5 weight % scope.In order to realize all even microdispersed distribution of pigment in styrene polymer, especially for the situation of polar pigment, it may be favourable using dispersion agent, for example organosilane, contain epoxide group polymkeric substance or with the styrene polymer of maleic anhydride graft.Preferred plasticizer is mineral oil, phthalic ester, the styrene-based polymkeric substance, and its consumption can be 0.05 to 10 weight %.
In order to produce expandable styrene polymer of the present invention, whipping agent is sneaked in the polymer melt.The method comprising the steps of a) produces melt, b) mixes c) cooling, d) transfer and e) granulating.In these steps each can be utilized in plastic working known equipment or equipment to make up and realize.Sneaking into melt can be by using static or dynamic mixing machine, and for example forcing machine is finished.Polymer melt can directly be taken from polymerization reactor, or can directly generate by the melt polymer particle in mixing forcing machine or in independent melt extruding in the machine.The cooling of melt can be finished in mixing equipment or in independent water cooler.The prilling process that is fit to for example is the granulation underwater of pressurization, and granulation is used rotary scraper and cooled off by spray atomization cooling liqs or atomizing atomizing granulation.The equipment setting that is fit to of carrying out this method for example is:
A) polymerization reactor-static mixer/water cooler-tablets press
B) polymerization reactor-forcing machine-tablets press
C) forcing machine-static mixer-tablets press
D) forcing machine-tablets press.
In addition, described setting can have the side forcing machine and be used to introduce additive, for example solid or thermo-responsive additive.
The styrene polymer melt that contains whipping agent in 140 to 300 ℃ temperature range, is preferably carried in 160 to 240 ℃ temperature range and is passed through machine head plate usually.Needn't be cooled to the second-order transition temperature zone.
Machine head plate is heated at least the temperature of the polystyrene melt that contains whipping agent.The temperature of machine head plate is preferably the high 20-100 of temperature ℃ than the polystyrene melt that contains whipping agent.This has prevented polymer deposition in die orifice, and guarantees accessible granulation.
In order to obtain salable granularity, in the exit of mould, the diameter in the hole in the mould (D) should be in 0.2 to 1.5mm scope, preferably in 0.3 to 1.2mm scope, especially preferably in 0.3 to 0.8mm scope.This makes in mode targetedly, even after die orifice swells, obtains the granularity less than 2mm, and especially the granularity in 0.4 to 1.4mm scope becomes possibility.
Die orifice swells and not only is subjected to the influence of molecular weight distribution, and is subjected to the influence of mould geometry.This machine head plate preferably has the L/D ratio and is at least 2 hole, and length (L) refers to that its diameter is in the zone in the hole that is not more than mould outlet place diameter (D).Ratio L/D is preferably in the 3-20 scope.
Usually, the diameter (E) that enters the hole at machine head plate place should be at least the twice of the diameter (D) in hole, mould outlet place.
In an embodiment of machine head plate, the hole has conical inlet and inlet angle α less than 180 °, preferably in 30 to 120 ° of scopes.In another embodiment, machine head plate has such hole, and this hole has flaring exit and exit angle β less than 90 °, preferably in 15 to 45 ° of scopes.For the targeted particle size that produces styrene polymer distributes, can provide the machine head plate that contains hole with different exit diameters (D).The use that also can be bonded to each other of the different embodiments of mould geometry.
The method of especially preferred production expandable styrene polymer may further comprise the steps:
If a) with styrene monomer and suitable copolymerisable monomer polymerization, form the styrene polymer of molecular-weight average in 160000 to 400000g/mol scopes,
B) the styrene polymer melt of acquisition is outgased,
C) at least 150 ℃, under preferred 180-260 ℃ the temperature, if whipping agent and suitable additive are sneaked in the styrene polymer melt by static or dynamic mixing machine,
D) the styrene polymer melt that will contain whipping agent is cooled at least 120 ℃, preferred 150-200 ℃ temperature,
E) introduce fire retardant by the side forcing machine,
F) by the discharging of tool foraminous machine head plate, this hole is not more than 1.5mm at the diameter at mould outlet place, and
G) will contain the fused mass granulating of whipping agent.
In step g), granulation can directly be carried out under the pressure of preferred 5 to 15 crust under water at 1 to 25 crust after machine head plate.
As the result who outgases in polymerization in the step a) and the step b), polymer melt can be directly used in and inject whipping agent in the step d), and the fusion styrene polymer is optional.This not only saves, and obtains having the expandable styrene polymer (EPS) of low-styrene monomer content, and this is that it causes being decomposed into monomer usually again because of the mechanical shearing effect of having avoided at the melt region of forcing machine.In order to keep the low-styrene monomer content, especially be lower than 500ppm, also advantageously in all processing steps subsequently, keep the input of mechanical energy and heat energy low as far as possible.For this reason, in step d) to f) in, especially preferred shearing rate is lower than 50/ second, preferred 5-30/ second, and temperature is lower than 260 ℃, and in 1 to 20 minute scope, preferred 2 to 10 minutes short retention time.In entire method, especially preferably only use static mixer and static water cooler.Polymer melt can shift and discharge by pressure pump (for example toothed gear pump).
Reduce other of content of styrene monomer content and/or residual solvent such as ethylbenzene may mode in step b), to outgas consumingly by entrainment agent such as water, nitrogen or carbonic acid gas, or in step a), carry out anionoid polymerization.This cinnamic anionoid polymerization not only causes styrene polymer to have the low-styrene monomer content, and causes styrene oligomer content low simultaneously.
When superoxide was used as fire retardant, the residual styrene content that contains the pill of whipping agent significantly reduced unexpectedly.When adding superoxide, observing molecular-weight average only has slight reduction, but does not find that the oligopolymer heat release significantly forms or monomer.At first, this makes and uses the polystyrene melt with higher residual monomer content to become possibility that this means that again this has reduced the degassing expense in styrene reactor downstream.The second, the previous residual monomer content of the polystyrene of the degassing in large quantities can further reduce.In this way, can obtain the EPS pill that residual monomer content is lower than 250ppm.
In order to improve processing characteristics, can use glyceryl ester, antistatic or anti-caking agent coating expandable styrene polymer pill finished product.
Can use glyceryl monostearate GMS (typically 0.25%), Tristearoylglycerol (typically 0.25%), silica Aerosil R972 in small, broken bits (typically 0.12%) and Zinic stearas (typically 0.15%) and static inhibitor apply the EPS pill.
Expandable styrene polymer pill produced according to the invention can form the foam beads of density in 8 to 100g/L scopes in the first step by warm air or steam pre-frothing, and fusion obtains foam molded articles in closed mould in second step.
Embodiment
Raw material:
(from the polystyrene of BASF AG, viscosity number VN is 83mL/g to PS148G, molecular-weight average M wBe 220000g/mol and polymolecularity M w/ M nBe 2.9).
(from the polystyrene of BASF AG, viscosity number VN is 98mL/g to PS158K, molecular-weight average M wBe 280000g/mol and polymolecularity M w/ M nBe 2.8).
HBCD: from the hexabromocyclododecane FR-1206 Hat (fire retardant) of Eurobrom
Retardant synergist:
Ditertiary butyl peroxide (Trigonox  B)
T-butyl hydroperoxide (Trigonox  A80)
Concentration is the pentane solution of the dicumyl peroxide of 50 weight %
Embodiment 1,2,4 and 5
The major ingredient stream (Skellysolve As of polystyrene 148G and 7 weight %) that will contain the polymer melt of whipping agent is cooled to 190 ℃ from 260 ℃, and is metered into and polystyrene melt premixed hexabromocyclododecane (HBCD) in the side forcing machine according to the details that table 1 (add-on is represented with the weight percentage based on polystyrene) provides.At equal height, be metered into retardant synergist by piston pump and metering spray gun.The polymer melt that obtains is carried with the through-put of 60kg/h and is passed the have 32 holes machine head plate of (diameter 0.75mm), and by the granulation underwater equipment granulation of pressurization, the compression pill that obtains having narrow size-grade distribution.
Embodiment 3 and 6
The details that provides according to table 1 repeats embodiment 1, uses viscosity number VN to be 98mL/g, molecular-weight average M wBe 280000g/mol and polymolecularity M w/ M nBe 2.8 polystyrene 158K from BASF AG.
Simultaneous test C1 to C5
Under the situation of not using HBCD and/or retardant synergist, repeat embodiment 1 or 6 (contrast experiment 2).
Embodiment 7
Repeat embodiment 1, changing part is that retardant synergist is metered into by the side forcing machine with fire retardant.
The expandable polystyrene pill that obtains pre-frothing in the materials flow of flowing produces the foam beads that density is about 20g/L, stores after 24 hours, by the steam fusion, obtains foams in the gastight mould.
After foams store 72 hours, measure combustionproperty.For this reason, in horizontal burning test, Bunsen flame is acted on 2 seconds of foams, subsequently these foams are removed from flame.Need less than afterfire time of 6 seconds with by B2 test according to DIN 4102.
The result and the viscosity number VN of amount of (being metered into) fire retardant and the combustion test of testing on the expansible polystyrene foam are summarized in the table 1.Table 2 be presented at embodiment 3 and 4 and simultaneous test C1 and C2 in foam performance.
Table 1:
Embodiment HBCD [weight %] Synergistic agent [weight %] Synergistic agent The afterfire time [second] PS VN Residual benzene ethene [ppm]
C1 - - - Burn down 148G 79 500
C2 - - - Burn down 158K 89 540
C3 - 0.4 TrigonoxA80 Burn down 148G
C4 - 0.4 TrigonoxB Burn down 148G
C5 1.5 - - Burn down 148G
1 1.5 0.4 TrigonoxB 0.5 148G
2 0.9 0.4 TrigonoxB 1.6 148G 219
3 0.6 0.2 TrigonoxB 3.8 158K 80 242
4 1.5 0.4 Trigonox80- 5.6 148G 74
5 0.6 0.2/0.2 TrigonoxA80/ TrigonoxB 2.8 148G
6 0.6 0.3 Dicumyl peroxide- 5.0 158K
7 0.6 0.4 TrigonoxB 14.0 148G
Table 2: tap density is with the variation of foamed time
Foamed time [second] C1 C2 Embodiment 3 Embodiment 4
2 20.0 21.0 18.6
4 16.1 22.4 16.5 13.2
5 19.2 12.5
6 13.5 18.5 13.9 13.5
8 14.7 16.7 14.8 15.2
10 17.9 15.6 17.7

Claims (6)

1. method of producing fp expandable styrene polymer (EPS) or fp styrene polymer exruded foams (XPS), wherein use organbromine compound as fire retardant, and use liquid peroxide, hydroperoxide or peroxide solutions as retardant synergist with at least 70 weight % bromine contents.
2. the method for claim 1 wherein uses ditertiary butyl peroxide, t-butyl hydroperoxide, dicumyl peroxide pentane solution or its mixture as retardant synergist.
3. method as claimed in claim 1 or 2 wherein uses hexabromocyclododecane as fire retardant.
4. as the method for each described production fp expandable styrene polymer (EPS) among the claim 1-3, wherein premix in the side forcing machine merges in the major ingredient stream that is metered into the styrene polymer melt that contains whipping agent with described fire retardant and a certain proportion of styrene polymer melt, and described retardant synergist is metered in the described major ingredient stream by pump, and the materials flow extruding that merges passed machine head plate, granulation underwater subsequently.
5. method as claimed in claim 4, the residence time under wherein said fire retardant and the retardant synergist melt temperature in 140 to 220 ℃ of scopes was less than 15 minutes.
6. method as claimed in claim 5, the residence time under wherein said fire retardant and the fire retardant synergistic agent melt temperature in 170 to 200 ℃ of scopes was less than 15 minutes.
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